JPH0320127B2 - - Google Patents
Info
- Publication number
- JPH0320127B2 JPH0320127B2 JP59216036A JP21603684A JPH0320127B2 JP H0320127 B2 JPH0320127 B2 JP H0320127B2 JP 59216036 A JP59216036 A JP 59216036A JP 21603684 A JP21603684 A JP 21603684A JP H0320127 B2 JPH0320127 B2 JP H0320127B2
- Authority
- JP
- Japan
- Prior art keywords
- acrylamide
- group
- chloride
- dimethylamino
- propyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920001577 copolymer Polymers 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 19
- 125000002091 cationic group Chemical group 0.000 claims description 14
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 8
- GDFCSMCGLZFNFY-UHFFFAOYSA-N Dimethylaminopropyl Methacrylamide Chemical compound CN(C)CCCNC(=O)C(C)=C GDFCSMCGLZFNFY-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 7
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- KFYRJJBUHYILSO-YFKPBYRVSA-N (2s)-2-amino-3-dimethylarsanylsulfanyl-3-methylbutanoic acid Chemical compound C[As](C)SC(C)(C)[C@@H](N)C(O)=O KFYRJJBUHYILSO-YFKPBYRVSA-N 0.000 claims description 2
- SSZXAJUPVKMUJH-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate;hydrochloride Chemical compound Cl.CN(C)CCOC(=O)C=C SSZXAJUPVKMUJH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002537 cosmetic Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- ADTJPOBHAXXXFS-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]prop-2-enamide Chemical compound CN(C)CCCNC(=O)C=C ADTJPOBHAXXXFS-UHFFFAOYSA-N 0.000 claims description 2
- 229950004354 phosphorylcholine Drugs 0.000 claims description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 1
- 239000001294 propane Substances 0.000 claims 1
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 37
- 239000000243 solution Substances 0.000 description 13
- 239000000835 fiber Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002453 shampoo Substances 0.000 description 2
- -1 softeners Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000008365 aqueous carrier Substances 0.000 description 1
- 239000008135 aqueous vehicle Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- SMVRDGHCVNAOIN-UHFFFAOYSA-L disodium;1-dodecoxydodecane;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC SMVRDGHCVNAOIN-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000006897 homolysis reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229920006029 tetra-polymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/12—Preparations containing hair conditioners
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/54—Polymers characterized by specific structures/properties
- A61K2800/542—Polymers characterized by specific structures/properties characterized by the charge
- A61K2800/5428—Polymers characterized by specific structures/properties characterized by the charge amphoteric or zwitterionic
Description
本発明はカオチン性両性四元共重合体、それら
のケラチン質繊維の処理への応用およびそれらを
含有する組成物に関する。
ケラチン質繊維を処理するための化粧品組成物
にアニオン成重合体、カチオン性重合体、アイオ
ノマーまたはそれらの混合物を使用することは知
られている。
それらの関心にもかかわらず、かかる組成物は
現在の消費者に望まれている品質の全てと原価と
を同時得ることができていない。
事実として特に毛髪の処理において、使用者は
最低の費用で、日常使用のため経時的に安定で、
かかる用途に普通使用するアニオン性界面活性剤
例えばラウリルエーテル硫酸ナトリウムと相溶性
であり、明るさを与え、しなやかで、ソフトタツ
チで、毛髪にふつくらとした形を与える組成物が
入手できることを望んでいる。
本発明者は消費者の要望に応じるケラチン質繊
維を処理するための組成物を見出した。
この目的は本発明による組成物に新規なカチオ
ン性水溶性両性四元共重合体を使用することによ
つて達成される。
本発明の目的であるこれらの新規なカチオン性
水溶性両性四元共重合体は下記一般式で非常に略
した方法で表わすことができる。
式中Ａは酸素原子またはNH基を表わし、Ｒは
ＡがNH基であるとき水素原子またはメチル基を
表わし、Ａが酸素原子であるとき水素原子のみを
表わす、ｎはＡが酸素原子であるとき２に等し
く、ＡはNH基であるとき３に等しい、ａ、ｂ、
ｃは使用した各単量体のモル百分率を表わし、下
記の関係に相当する。
ａ＋2b＋ｃ＝100
30＜ａ＜75
10＜ｂ＜25
５＜ｃ＜20
更に詳細には本発明の目的は、下記のモル百分
率を有する４種の下記の群の単量体に属する４種
の既知の重合体のそれ自体知られている方法によ
る共重合体により生成する上述した如き四元共重
合体にある。
１ ａ％のアクリルアミド（AAM）、
２ ｂ％の２−アクリルアミド−２−メチル−プ
ロパンスルホン酸（AMPS）、
３ ｂ％の下記３種の単量体の中から選択した塩
基性単量体、
ジメチルアミノエチルアクリレート
（ADAME）Ｎ−（３−ジメチルアミノ−１−
プロピル）−アクリルアミド（DMAPA）、
Ｎ−（３−ジメチルアミノ−１−プロピル）−
メタクリルアミド（DMAPMA）、
４ ｃ％の下記４種の単量体の中から選択したカ
チオン性単量体、
Ｎ，Ｎ，Ｎ−３−トリメチルアクリルアミド
−プロパンアミニウムクロライド（APTAC）、
Ｎ，Ｎ，Ｎ−３−トリメチルメタクリルアミド
−プロパンアミニウムクロライド
（MAPTAC）、Ｎ，Ｎ，Ｎ−２−トリメチルア
クリロイルオキシ−エタンアミニウムクロライ
ド（CMA）、ジメチルアミノエチルアクリレー
トハイドロクロライド（CHA）。
（なおａ、ｂ、ｃは上述した意義を有する）。
このことは、本発明によるカチオン性両性四
元共重合体は、アクリルアミドのモル％が30〜
75％の間にあり、２−アクリルアミド−２−メ
チル−プロパンスルホン酸と塩基性単量体のモ
ル％は等しくかつ10〜25％の間にあり、カチオ
ン性単量体のモル％は５〜20％の間にあること
を意味する。
本発明の目的は特に、
(1) 四元共重合体が、モル割合で75％のアクリル
アミド、10％の２−アクリルアミド−２−メチ
ル−プロパンスルホン酸、10％のＮ−（３−ジ
メチルアミノ−１−プロピル）−メタクリルア
ミドおよび５％のＮ，Ｎ，Ｎ−３−トリメチル
メタクリルアミド−プロパンアミニウムクロラ
イドを含有する上記一般式の定義に相当する四
元共重合体；および
(2) 四元共重合体が、モル割合で40％のアクリル
アミド、20％の２−アクリルアミド−２−メチ
ル−プロパンスルホン酸、20％のＮ−（３−ジ
メチルアミノ−１−プロピル）−メタクリレー
ト、および20％のＮ，Ｎ，Ｎ−３−トリメチル
メタクリルアミド−プロパンアミニウムクロラ
イドを含有する上記一般式の定義に相当する四
元共重合体
にある。
これらの酸性、塩基性またはアミニウム単量体
とアクリルアミドとの反応性比r1およびr2は、
AAM−AMPSのカツプルについてはr1＝１およ
びr2＝0.52（J.POLYMER Sci.C、1982年第20巻
第817頁〜第838頁）、造塩または四級化された
AAM−ADMEカツプルについてはr1＝0.7〜08お
よびr2＝0.55〜0.66（米国特許第396 752号）、
AAM−DMAPMAカツプルについてはr1＝0.47
およびr2＝0.98、そしてAAM−MAPTACカツ
プルについてはr1＝0.51およびr2＝1.08（J.
POLYMER Sci.C、1977年第15巻第3047頁〜第
3074頁）で均質共重合するのが有利である。
本発明による四元共重合体は、存在するエステ
ル官能基の加水分解を防ぐため、一般に４〜５の
僅かに酸性のPHで、不活性雰囲気とした水性の均
質脱酸素化相でラジカル共重合によつて上述した
単量体から容易に得られる。
単量体Cp中の初期重量濃度は10〜40％で変化さ
せることができ、過硫酸アンモニウムの如き熱ホ
モリシスによつて作用する通常の水溶性開始剤を
使用できる。
共重合は一般に約60〜80℃で加熱して行ない、
次いで反応が完了したとき、予め常温に冷却した
水性反応溶液を必要ならば稀薄アンモニアでPH
6.7に中和し、最後に得られた溶液をできるなら
通常美容術で使用される濃度で既知の殺菌剤およ
び殺カビ剤を添加して保護する。
かくして得られた水性溶液中の四元共重合体
は、塩化ナトリウムの１モル溶液中で20℃で測定
して１〜５dl／ｇの固有粘度を与える。共重合の
開始剤割合およびCpを変えることによつて、ケラ
チン質繊維を処理するのに有用である本発明によ
る四元共重合体の水性溶液のため、高個有粘度ま
たは低個有粘度の何れでも所望に応じて得ること
ができるが、それは繊維を効果的に湿潤させるの
に充分な流動性と、繊維上に残るのに充分な粘性
であることが必要である。
実験では、本発明による組成物または配合物中
に混入すべき本発明による四元共重合体の量は、
達成すべき所望の特定結果によつて決る。一般に
この量は、水性組成物の全重量の対して乾燥材料
で表わしたとき約0.1〜５重量％台の割合を構成
しなければならない。
本発明によるカチオン性水溶性両性四元共重合
体は本発明による組成物の必須活性成分を構成す
るが、かかる組成物はまたその付与を容易にで
き、あるいは嗅覚性を改良することのできる他の
成分も含有できる。
従つて例えば香料、組成物それ自体もしくはケ
ラチン質繊維を着色する機能を有する着色剤、防
腐剤、金属封鎖剤、粘稠剤、軟化剤、発泡剤、発
泡安定剤、太陽光フイルター、解膠剤のみならず
カチオン、アニオン、両性、ノニオン界面活性剤
またはそれらの混合物の如きかかる組成物に普通
のもしくは知られている構成成分の１種以上を本
発明による組成物中に混入することも本発明の範
囲で好適である。
本発明による組成物と組合せるキヤリヤーまた
はビヒクルは水性ビヒクルまたはキヤリヤーであ
る。かかる組成物は任意の形態、溶液、乳濁液ま
たは水性ゲル等をとることができる。
本発明による組成物は例えばヘヤケアーのため
に好適な任意の方法でケラチン質繊維の処理に適
用でき、通常の方法は実施例に示す如く、シヤン
プーで洗つた髪に数分間本発明による組成物を付
与し、次いで櫛でけずる前に髪を水洗することか
らなる。
ケラチン質繊維に付与するとき本発明による組
成物の量は使用者の要望に応じた割合で変えるこ
とができるが、一般には処理すべきケラチン質繊
維の重量の１％より少なくてはならず20％を越え
てはならない。
ケラチン質繊維における本発明による四元共重
合体の効果は、それらを含有する組成物から得ら
れる数回の簡単な試験で容易に決定できる。
かかる試験の中幾つかは、市販のシヤンプーで
予め洗つた髪の房を、次いで本発明による組成物
で湿らせ処理し、次いで目で髪の湿りについて得
られた効果を観察し、その後乾燥し、軟らかさ、
輝き、柔軟性、挙動、非電気的性質、付与容易
性、得られた髪の嵩について観察するのである。
別の試験では、ATNM D1173−53に記載され
ている試験で、本発明による組成物の発泡性を決
定できる。
最後に、本発明による四元共重合体0.5重量％
を含有する水性溶液の常温での時間安定性を、美
容品で普通に使用される既知の殺菌剤および殺カ
ビ剤の混合物0.07重量％の存在下に60日間20℃で
日光の下で貯蔵したかかる溶液のブルツクフイー
ルド粘度を追求して調査した。かかる溶液のブル
ツクフイールド粘度の著しい変化は見られなかつ
た、更にそれらは完全に透明なままであつた。
本発明の他の利点および特性は以下の説明およ
び実施例（これは例示のため示し、限定するもの
ではない）から明らかであろう。
実施例 １
モル割合で40／20／20／20のAAM−AMPS−
DMAPMA−MAPTACのカチオン性両性四元共
重合体の製造。
29.39（0.142モル）のAMPS、24.14ｇ
（0.142モル）のDMAPMA、20.16ｇ（0.284モル）
のAAM、31.31ｇ（0.142モル）のMAPTAC、
0.787ｇ（3.45モル）の過硫酸アンモニウム、595
ｇの水を含有し、完全に酸素を除いた水性溶液
を、窒素雰囲気中で、１〜1.5℃／分の速度で反
応容器中で20℃から80℃に加熱した。
反応は約60℃で開始し、溶液の温度が80℃に達
したとき、この温度で１時間保ち、次いで80℃
で、５ｇの水中の溶液の形で0.262ｇ（1.5ｍモ
ル）の過硫酸アンモニウムを導入し、加熱を80℃
で更に１時間、85〜90℃で30分続けた。次いで溶
液を常温に冷却し、その後溶液のPHを20％稀薄ア
ンモニアで6.5〜7.0にした。
かくして軸２を用い、20rpmで20℃で測定した
とき0.36Pa・ｓのブルツクフイールド粘度を示
し、モル割合で40／20／20／20であり、塩化ナト
リウムの１モル溶液中で20℃で測定したとき1.01
dl／ｇの固定粘度を有するAAM−AMPS−
DMAPMA−MAPTACのカチオン性両性四元重
合体15.5重量％を含有する水性溶液が得られた。
実施例 ２〜６
実施例１の方法に従つたが、表に示した如き
単量体のモル割合で出発して、100ｇについての
ｇ数で表わし、140℃で１時間１ｇの試料を乾燥
して測定したMA濃度を有するカチオン性両性水
溶性四元共重合体を含有する水性溶液を得た。こ
れらの水性溶液は、表に示す如き20rpmで回転
する軸２を有するブルツクフイールド粘度計で20
℃で測定し、mPa／ｓで表わしたブルツクフイ
ールド粘度を示した。また得られた四元共重合体
の固有粘度〔η〕も表に示す。かかる粘度は塩
化ナトリウムの１モル溶液中で25℃で測定した。
残存単量体の含量体は残存エチレン結合の通常
の量で測定した。それは溶液100ｇについてのｇ
数で表わす。
The present invention relates to cationic amphoteric quaternary copolymers, their application in the treatment of keratinous fibers and compositions containing them. It is known to use anionic polymers, cationic polymers, ionomers or mixtures thereof in cosmetic compositions for treating keratinous fibers. Despite their interest, such compositions do not offer the full range of quality and cost desired by today's consumers. The fact is that, especially in the treatment of hair, the user can use products that are stable over time for daily use and at the lowest cost.
It would be desirable to have a composition that is compatible with the anionic surfactants commonly used in such applications, such as sodium lauryl ether sulfate, and that imparts lightness, suppleness, soft touch, and fullness to the hair. There is. The inventor has discovered a composition for treating keratinous fibers that meets consumer demands. This object is achieved by using novel cationic water-soluble amphoteric quaternary copolymers in the compositions according to the invention. These novel cationic water-soluble amphoteric quaternary copolymers which are the object of the present invention can be represented in a very abbreviated manner by the following general formula. In the formula, A represents an oxygen atom or an NH group, R represents a hydrogen atom or a methyl group when A is an NH group, and represents only a hydrogen atom when A is an oxygen atom, and n represents A when A is an oxygen atom. equals 2 when A is an NH group, equals 3 when a, b,
c represents the molar percentage of each monomer used and corresponds to the following relationship. a+2b+c=100 30<a<75 10<b<25 5<c<20 More particularly, the object of the invention is to obtain four known monomers belonging to the following groups of monomers having the following molar percentages: The above-mentioned quaternary copolymers are produced by copolymerizing the polymers of 1 a% acrylamide (AAM), 2 b% 2-acrylamido-2-methyl-propanesulfonic acid (AMPS), 3 b% a basic monomer selected from the following three monomers, Dimethylaminoethyl acrylate (ADAME) N-(3-dimethylamino-1-
propyl)-acrylamide (DMAPA), N-(3-dimethylamino-1-propyl)-
Methacrylamide (DMAPMA), 4 c% of a cationic monomer selected from the following four types of monomers, N,N,N-3-trimethylacrylamide-propanaminium chloride (APTAC),
N,N,N-3-trimethylmethacrylamide-propanaminium chloride (MAPTAC), N,N,N-2-trimethylacryloyloxy-ethanaminium chloride (CMA), dimethylaminoethyl acrylate hydrochloride (CHA). (Note that a, b, and c have the meanings described above). This means that the cationic amphoteric quaternary copolymer according to the present invention has an acrylamide mole percentage of 30 to 30%.
75%, the mol% of 2-acrylamido-2-methyl-propanesulfonic acid and basic monomer are equal and between 10-25%, and the mol% of cationic monomer is between 5-25%. This means that it is between 20%. In particular, the object of the present invention is to provide (1) a quaternary copolymer containing, in molar proportions, 75% acrylamide, 10% 2-acrylamido-2-methyl-propanesulfonic acid, and 10% N-(3-dimethylamino -1-propyl)-methacrylamide and 5% of N,N,N-3-trimethylmethacrylamide-propanaminium chloride, a quaternary copolymer corresponding to the definition of the general formula above; and (2) The original copolymer contains, in molar proportions, 40% acrylamide, 20% 2-acrylamido-2-methyl-propanesulfonic acid, 20% N-(3-dimethylamino-1-propyl)-methacrylate, and 20% It is a quaternary copolymer corresponding to the definition of the above general formula containing N,N,N-3-trimethylmethacrylamide-propanaminium chloride. The reactivity ratios r 1 and r 2 of these acidic, basic or aminium monomers with acrylamide are:
r 1 = 1 and r 2 = 0.52 for AAM-AMPS couplets (J.POLYMER Sci.C, 1982, Vol. 20, pp. 817-838),
r 1 = 0.7-08 and r 2 = 0.55-0.66 for the AAM-ADME couple (U.S. Pat. No. 396,752);
For the AAM−DMAMAP couple, r 1 = 0.47
and r 2 = 0.98, and r 1 = 0.51 and r 2 = 1.08 for the AAM-MAPTAC couple (J.
POLYMER Sci.C, 1977, Volume 15, Pages 3047-No.
It is advantageous to carry out homogeneous copolymerization (page 3074). The quaternary copolymers according to the invention are radically copolymerized in an aqueous homogeneous deoxygenated phase in an inert atmosphere, generally at a slightly acidic pH of 4 to 5 to prevent hydrolysis of the ester functional groups present. can be easily obtained from the monomers mentioned above. The initial weight concentration in monomer C p can be varied from 10 to 40% and conventional water-soluble initiators acting by thermal homolysis such as ammonium persulfate can be used. Copolymerization is generally carried out by heating at about 60 to 80°C.
Then, when the reaction is complete, the aqueous reaction solution, previously cooled to room temperature, is PH'd with dilute ammonia if necessary.
6.7 and the finally obtained solution is protected by addition of known bactericides and fungicides, preferably in concentrations normally used in cosmetology. The quaternary copolymer in aqueous solution thus obtained gives an intrinsic viscosity of 1 to 5 dl/g, measured at 20 DEG C. in a 1 molar solution of sodium chloride. By varying the initiator proportion and C p of the copolymerization, high or low individual viscosities can be obtained for the aqueous solutions of the quaternary copolymers according to the invention, which are useful for treating keratinous fibers. can be obtained as desired, provided that it is sufficiently fluid to effectively wet the fibers and sufficiently viscous to remain on the fibers. Experiments have shown that the amount of quaternary copolymer according to the invention to be incorporated into the composition or formulation according to the invention is
It depends on the specific results desired to be achieved. Generally, this amount should constitute on the order of about 0.1 to 5% by weight, expressed as dry material, based on the total weight of the aqueous composition. Although the cationic water-soluble amphoteric quaternary copolymers according to the invention constitute an essential active ingredient of the compositions according to the invention, such compositions can also be used to facilitate their application or to improve their olfactory properties. It can also contain the following ingredients. Thus, for example, fragrances, colorants having the function of coloring the composition itself or the keratinous fibers, preservatives, sequestrants, thickeners, softeners, blowing agents, foam stabilizers, solar filters, deflocculants. It is also within the scope of the present invention to incorporate into the compositions according to the invention one or more of the usual or known constituents of such compositions, such as cationic, anionic, amphoteric, nonionic surfactants or mixtures thereof. It is suitable within the range of . The carrier or vehicle with which the composition according to the invention is combined is an aqueous vehicle or carrier. Such compositions can take any form, such as a solution, emulsion or aqueous gel. The compositions according to the invention can be applied to the treatment of keratinous fibers in any manner suitable for example for hair care; the usual method is to apply the compositions according to the invention to shampoo-washed hair for a few minutes, as shown in the examples. It consists of applying and then washing the hair before combing. The amount of the composition according to the invention when applied to keratinous fibers can vary in proportions depending on the wishes of the user, but generally should not be less than 1% of the weight of the keratinous fibers to be treated. Must not exceed %. The effectiveness of the quaternary copolymers according to the invention on keratinous fibers can be easily determined in a few simple tests obtained from compositions containing them. In some such tests, locks of hair, previously washed with a commercially available shampoo, were then moistened and treated with the composition according to the invention, and the effect obtained on the wetting of the hair was then visually observed, and then dried. , softness,
Observe the shine, flexibility, behavior, non-electrical properties, ease of application, and the resulting bulk of the hair. In another test, the foaming properties of the compositions according to the invention can be determined in the test described in ATNM D1173-53. Finally, 0.5% by weight of the quaternary copolymer according to the invention
The time stability at normal temperature of an aqueous solution containing 0.07 wt. The Bruckfield viscosity of such a solution was investigated. No significant change in the Bruckfield viscosity of such solutions was observed; furthermore, they remained completely clear. Other advantages and characteristics of the invention will be apparent from the following description and examples, which are given by way of illustration and not by way of limitation. Example 1 AAM-AMPS- with a molar ratio of 40/20/20/20
Production of cationic amphoteric quaternary copolymer of DMAPMA-MAPTAC. 29.39 (0.142 mol) AMPS, 24.14 g
(0.142 mol) of DMAPMA, 20.16 g (0.284 mol)
of AAM, 31.31 g (0.142 mol) of MAPTAC,
0.787 g (3.45 mol) ammonium persulfate, 595
A completely deoxygenated aqueous solution containing 100 g of water was heated in a reaction vessel from 20°C to 80°C at a rate of 1-1.5°C/min in a nitrogen atmosphere. The reaction started at about 60°C, and when the temperature of the solution reached 80°C, it was kept at this temperature for 1 hour and then increased to 80°C.
0.262 g (1.5 mmol) of ammonium persulfate was introduced in the form of a solution in 5 g of water and heating was carried out at 80 °C.
The temperature was then continued for another hour at 85-90°C for 30 minutes. The solution was then cooled to room temperature, after which the pH of the solution was brought to 6.5-7.0 with 20% dilute ammonia. It thus exhibits a Bruckfield viscosity of 0.36 Pa·s when measured at 20°C at 20 rpm using axis 2 and has a molar ratio of 40/20/20/20 in a 1 molar solution of sodium chloride at 20°C. 1.01 when measured
AAM-AMPS- with fixed viscosity of dl/g
An aqueous solution containing 15.5% by weight of a cationic amphoteric tetrapolymer of DMAPMA-MAPTAC was obtained. Examples 2-6 Following the method of Example 1, but starting with the molar proportions of monomers as shown in the table, 1 g of sample was dried at 140° C. for 1 hour, expressed in grams per 100 g. An aqueous solution was obtained containing a cationic amphoteric water-soluble quaternary copolymer having an MA concentration measured as follows. These aqueous solutions were tested at 20°C in a Bruckfield viscometer with shaft 2 rotating at 20rpm as shown in the table.
The Bruckfield viscosity was measured at °C and expressed in mPa/s. The table also shows the intrinsic viscosity [η] of the obtained quaternary copolymer. Such viscosities were determined in 1 molar solutions of sodium chloride at 25°C. The residual monomer content was determined by the usual amount of residual ethylene bonds. It is g for 100g of solution
Expressed in numbers.
【表】
実施例 ７〜15
(A) 髪を処理するための組成物の製造。
実施例１〜６に記載した如きカオチン性両性
水溶液四元共重合体の水性溶液から、番号７〜
14の髪を処理するための水性組成物を作つた。
かかる組成物中の各成分の活性乾燥材料の重
量％を表に示す。
組成物15は参考組成物である。Table: Examples 7-15 (A) Preparation of compositions for treating hair. From the aqueous solutions of cationic amphoteric quaternary copolymers as described in Examples 1-6, numbers 7-
14 made an aqueous composition for treating hair. The weight percent active dry material of each component in such compositions is shown in the table. Composition 15 is a reference composition.
【表】【table】
【表】
(B) 予めシヤンプーで洗つた髪をしめらせ、次い
で乾燥した髪についての組成物の効果。
予めシヤンプーで洗つた湿らせた髪について
の本発明による組成物の効果を肉眼試験で測定
し、観察された効果の関数として、１〜５から
の組成物を下記コードに従つて評価した。
非常にすぐれている ：５
良 好 ：４
平均的 ：３
少し悪し ：２
悪 し ：１
得られた結果を表に示す。
同様に髪を一度乾燥して組成物を試験した、
これらの効果の肉眼観察を表に示す。Table: (B) Effect of the composition on pre-washed hair, moisturized and then dried. The effect of the compositions according to the invention on damp hair, previously washed with shampoo, was determined in a visual test and, as a function of the observed effect, the compositions from 1 to 5 were evaluated according to the code below. Very good: 5 Good: 4 Average: 3 Slightly poor: 2 Poor: 1 The results obtained are shown in the table. Similarly, the composition was tested by drying the hair once.
Visual observations of these effects are shown in the table.
【表】【table】
【表】
(C) 組成物の発泡力の測定
一定組成物の発泡力は、水道水で３％（重
量）に組成物を稀釈後ASTM D1173−53に従
つて40℃で測定した。表に試験した組成物に
ついての分で表わした時間の関数としてcmで表
わした泡の高さを示す。Table (C) Determination of foaming power of compositions The foaming power of certain compositions was measured at 40° C. according to ASTM D1173-53 after diluting the composition to 3% (by weight) with tap water. The table shows the foam height in cm as a function of time in minutes for the compositions tested.
Claims (1)
ＡがNH基を表わすとき水素原子またはメチル基
を表わし、Ａが酸素原子を表わすとき水素原子の
みを表わす、ｎはＡが酸素原子を表わすとき２に
等しく、ＡがNH基を表わすとき３に等しい、
ａ、ｂおよびｃは使用した各単量体のモル百分率
を表わし、下記関係 ａ＋2b＋ｃ＝100 30＜ａ＜75 10＜ｂ＜25 ５＜ｃ＜20 に相当する）を有し、塩化ナトリウムの１モル溶
液中で20℃で測定した固有粘度が１〜５dl／ｇで
ある化粧品用カチオン性両性水溶性四元共重合
体。 ２ ａモルのアクリルアミド（AAM）；ｂモル
の２−アクリルアミド−２−メチル−プロパンス
ルホン酸（AMPS）；ｂモルのジメチルアミノエ
チルアクリレート（ADAME）、Ｎ−（３−ジメ
チルアミノ−１−プロピル）アクリルアミド
（DMAPA）およびＮ−（３−ジメチルアミノー
１−プロピル）メタクリルアミド（DMAPMA）
の３種の単量体から選択した塩基性単量体；ｃモ
ルのＮ，Ｎ，Ｎ−３−−トリメチルアクリルアミ
ド−プロパンアミニウムクロライド（APTAC）、
Ｎ，Ｎ，Ｎ−３−トリメチルメタクリルアミド−
プロパンアミニウムクロライド（MAPTAC）、
Ｎ，Ｎ，Ｎ−２−トリメチルアクリロイルオキシ
−エタンアミニウムクロライド（CMA）、および
ジメチルアミノエチルアクリレートハイドロクロ
ライド（CHA）の４種の単量体から選択したカ
チオン性単量体（ただし ａ＋2b＋ｃ＝100 30＜ａ＜75 10＜ｂ＜25 ５＜ｃ＜20 の関係にある）の共重合から得られる特許請求の
範囲第１項記載のカチオン性両性水溶性四元共重
合体。 ３ モル割合で、75％のアクリルアミド、10％の
２−アクリルアミド−２−メチル−プロパンスル
ホン酸、10％のＮ−（３−ジメチルアミノ−１−
プロピル）−メタクリルアミド、および５％のＮ，
Ｎ，Ｎ−３−トリメチルメタクリルアミド−プロ
パンアミニウムクロライドを含有する特許請求の
範囲第１項記載の四元共重合体。 ４ モル割合で、40％のアクリルアミド、20％の
２−アクリルアミド−２−メチル−プロパンスル
ホン酸、20％のＮ−（３−ジメチルアミノ−１−
プロピル）−メタクリルアミドおよび20％のＮ，
Ｎ，Ｎ−３−トリメチルメタクリルアミド−プロ
パンアミニウムクロライドを含有する特許請求の
範囲第１項記載の四元共重合体。[Claims] 1. The following general structural formula (In the formula, A represents an oxygen atom or an NH group, R represents a hydrogen atom or a methyl group when A represents an NH group, and represents only a hydrogen atom when A represents an oxygen atom, and n represents an oxygen atom when A represents an oxygen atom. equal to 2 when A represents an NH group, and equal to 3 when A represents an NH group,
a, b and c represent the molar percentage of each monomer used, and have the following relationship: a+2b+c=100 30<a<75 10<b<25 5<c<20), and 1 of sodium chloride A cationic amphoteric water-soluble quaternary copolymer for cosmetics having an intrinsic viscosity of 1 to 5 dl/g measured in molar solution at 20°C. 2 a mol of acrylamide (AAM); b mol of 2-acrylamido-2-methyl-propanesulfonic acid (AMPS); b mol of dimethylaminoethyl acrylate (ADAME), N-(3-dimethylamino-1-propyl) Acrylamide (DMAPA) and N-(3-dimethylamino-1-propyl)methacrylamide (DMAPMA)
A basic monomer selected from three types of monomers; cmole of N,N,N-3-trimethylacrylamide-propanaminium chloride (APTAC);
N,N,N-3-trimethylmethacrylamide-
Propane aminium chloride (MAPTAC),
A cationic monomer selected from four types of monomers: N,N,N-2-trimethylacryloyloxy-ethanaminium chloride (CMA) and dimethylaminoethyl acrylate hydrochloride (CHA) (where a+2b+c=100 30 < a < 75 10 < b < 25 5 < c < 20 ). 3 In molar proportions, 75% acrylamide, 10% 2-acrylamido-2-methyl-propanesulfonic acid, 10% N-(3-dimethylamino-1-
propyl)-methacrylamide, and 5% N,
The quaternary copolymer according to claim 1, which contains N,N-3-trimethylmethacrylamide-propanaminium chloride. 4 In molar proportions, 40% acrylamide, 20% 2-acrylamido-2-methyl-propanesulfonic acid, 20% N-(3-dimethylamino-1-
propyl)-methacrylamide and 20% N,
The quaternary copolymer according to claim 1, which contains N,N-3-trimethylmethacrylamide-propanaminium chloride.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8316621A FR2553779B1 (en) | 1983-10-19 | 1983-10-19 | CATIONIC AMPHOLYTE TETRAPOLYMERS, THEIR APPLICATION IN THE TREATMENT OF KERATINIC FIBERS AND COMPOSITIONS CONTAINING THEM |
| FR8316621 | 1983-10-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60108409A JPS60108409A (en) | 1985-06-13 |
| JPH0320127B2 true JPH0320127B2 (en) | 1991-03-18 |
Family
ID=9293292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59216036A Granted JPS60108409A (en) | 1983-10-19 | 1984-10-15 | Cationic amphoteric quaternary polymer and cosmetic composition |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4590249A (en) |
| EP (1) | EP0139588B1 (en) |
| JP (1) | JPS60108409A (en) |
| DE (1) | DE3464498D1 (en) |
| FR (1) | FR2553779B1 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61197008A (en) * | 1985-02-27 | 1986-09-01 | Mitsubishi Chem Ind Ltd | Anionic flocculant for waste water containing fine mineral particles |
| JPH0657240B2 (en) * | 1985-10-31 | 1994-08-03 | アイコ−株式会社 | Deodorant |
| US4837013A (en) * | 1986-10-24 | 1989-06-06 | Gaf Corporation | Quaternized nitrogen containing compounds |
| EP0288553A4 (en) * | 1986-10-24 | 1991-08-07 | Gaf Corporation | Composition used in permanent alteration of hair color |
| US4871535A (en) * | 1986-10-24 | 1989-10-03 | Gaf Corporation | Compositions used in permanent structure altering of hair |
| CA2072175A1 (en) * | 1991-06-28 | 1992-12-29 | Shih-Ruey T. Chen | Ampholyte terpolymers providing superior conditioning properties in shampoos and other hair care products |
| NZ243274A (en) * | 1991-06-28 | 1994-12-22 | Calgon Corp | Hair care compositions containing ampholytic terpolymers |
| US5338541A (en) * | 1992-10-15 | 1994-08-16 | Calgon Corporation | Dual cationic terpolymers providing superior conditioning properties in hair, skin and nail care products |
| FR2742657B1 (en) * | 1995-12-21 | 1998-01-30 | Oreal | COMPOSITIONS FOR THE TREATMENT OF KERATINIC MATERIALS COMPRISING THE ASSOCIATION OF A POLYAMPHOLYTE POLYMER AND A CATIONIC POLYMER |
| WO2002032538A1 (en) * | 2000-10-13 | 2002-04-25 | Japan Alsi Co., Ltd. | Flocculants for oil-water separation and method for oil-water separation by flocculation |
| US7012048B2 (en) * | 2003-02-11 | 2006-03-14 | National Starch And Chemical Investment Holding Corporation | Composition and method for treating hair containing a cationic ampholytic polymer and an anionic benefit agent |
| AU2003260455A1 (en) * | 2003-08-25 | 2005-04-11 | Merz Pharma Gmbh And Co. Kgaa | Detergent-containing preparation with a combination of polysaccharide polymers and tetra-copolymers and use thereof for example for personal cleaning |
| JP5427984B2 (en) * | 2009-01-05 | 2014-02-26 | 三菱レイヨン株式会社 | Sulfonic acid group-containing amphoteric water-soluble polymer aqueous solution and process for producing the same |
| CN101864031A (en) * | 2010-05-07 | 2010-10-20 | 华南理工大学 | Method for preparing temperature control variable viscosity acid gelating agent by aqueous solution polymerization |
| KR102387338B1 (en) * | 2016-03-14 | 2022-04-15 | 아이에스피 인베스트먼츠 엘엘씨 | Personal Care Compositions for Keratin Substrates Containing Conditioning, Color Protecting and Styling Polymers |
| FR3105736B1 (en) | 2019-12-27 | 2022-08-26 | S N F Sa | TRANSPARENT COMPOSITION FOR HAIR AND/OR SKIN CARE |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS536214B2 (en) * | 1972-08-24 | 1978-03-06 | ||
| GB1510689A (en) * | 1974-12-19 | 1978-05-10 | Sumitomo Chemical Co | Preparation of water-soluble cationic high polymer |
| US4171418A (en) * | 1977-11-22 | 1979-10-16 | American Cyanamid Company | Cationic and amphoteric surfactants |
| CH645653A5 (en) * | 1980-08-01 | 1984-10-15 | Ciba Geigy Ag | QUATERNAERE, COPOLYMERE, HIGH MOLECULAR AMMONIUM SALTS ON ACRYLIC BASE, THE PRODUCTION AND USE THEREOF AS ACTIVE COMPONENTS IN COSMETIC AGENTS. |
-
1983
- 1983-10-19 FR FR8316621A patent/FR2553779B1/en not_active Expired
-
1984
- 1984-10-10 US US06/659,539 patent/US4590249A/en not_active Expired - Lifetime
- 1984-10-11 DE DE8484402047T patent/DE3464498D1/en not_active Expired
- 1984-10-11 EP EP84402047A patent/EP0139588B1/en not_active Expired
- 1984-10-15 JP JP59216036A patent/JPS60108409A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| EP0139588A2 (en) | 1985-05-02 |
| DE3464498D1 (en) | 1987-08-06 |
| FR2553779A1 (en) | 1985-04-26 |
| FR2553779B1 (en) | 1986-02-21 |
| EP0139588B1 (en) | 1987-07-01 |
| US4590249A (en) | 1986-05-20 |
| EP0139588A3 (en) | 1985-06-05 |
| JPS60108409A (en) | 1985-06-13 |
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